Preparation of carbon disulfide



Sept. 18, 1951 H. o. FoLKlNs ETAL PREPARATION OF CARBON DISULF'IDE Filed March 18, 1948 3. Sheets-Sheet l H. o. FoLKlNs ETAL 2,568,121

PREPARATION oF CARBON DISULFIDE 3 Sheets-Sheet Z Sept 18, 1951 Filed March 18, 1948 Sept. 18, 1951 H50. FoLKlNs ETAL 2,563,121

PREPARATION 0F CARBON DISULFIDE Filed March 18, 1948 3 Sheets-Sheet 3 Patented Sept. 18, 1951 PREPARATION CARBON DISULFIDE Hillis 0. Folkins, Skokie, Charles A. Porter, Crystal Lake, and Elmer Miller and Harvey Hennig, Evanston, Ill., assignors to The Pure Oil Company, Chicago, Ill., a corporation of Ohio Application March 18, 1948, Serial No. 15,664

Claims. l to method and apparatus disulfide from hydrocar- This invention relates for synthesizing carbon bon gas and sulfur.

An object of the invention is to provide a novel method and apparatus for superheating sulfur vapors prior to charging them to a catalytic reaction zone.

Another object of the invention is to provide method and apparatus for conducting the synthesis of carbon disulfide from sulfur vapor and hydrocarbon gas under adiabatic conditions.`

Still another object of the invention is to provide method and apparatus for separating nely divided sulfur particles and sulfur vapor from the reaction products of a carbon disulfide op-V eration.

Other objects of the invention will manifest themselves from the following description and the accompanying drawing of which Figure 1 is a diagrammatic elevational view of the feed preparation section of apparatus useful for carrying out the process of this invention;

Figure 2 is a .diagrammatic elevational viewl of the heater, reactor and sulfur recovery section of apparatus useful in carrying out the invention; and

Figure 3 is a diagrammatic elevational View of the product recovery section of the apparatus.

Referring now to Figure 1, the numeral I indicates a line controlled by valve 3 for charging gas to the process. The gas charged under pressure through line I may be natural gas or renery gas or manufactured gas, preferably having a high content of methane. The charging gas passes to the lower portion of an absorber 5 f and passes upwardly therethrough in contact with a countercurrent stream of lean absorber oil such as light gas oil, kerosene or naphtha. The absorber 5 may be lled between the gas inlet I and the lean absorber oil inlet pipe 1 with contacting surfaces 9 such as Raschig rings. It will be understood that any other vapor-liquid contacting devices, such as bubble plates, may be used instead of Raschig rings. The absorber is preferably maintained under pressure of approximately 50 to 125 pounds per square inch gauge. In the absorber 5 the major portion of those hydrocarbons having three (3) or more carbon atoms in the molecule are absorbed so that the gas leaving the top of the absorber through line II contains 1% or less of C4 and higher molecular Weight hydrocarbons, 96% or more of C1 and C2 hydrocarbons, the total C2 hydrocarbon content of the gas being not more than about 10% and the C3 hydrocarbon content being not over 4%.

The fat absorber oil leaves the bottom of the absorber through line I3, passes through an indirect heat exchanger I5, an indirect steam heater IT. and then is sent to the upper portion of stripper 2 f I9. In passing through heat exchanger I5 and heater I1, the fat oil is heated to a temperature in the range of approximately 200-350 F., de.` pendent upon operating conditions and type of Y absorption oil used, in order to strip the absorbed gas from the absorption oil. Pressure in the line I3 may be reduced at valve 2| to approximately atmospheric pressure. .The fat voil passes downwardly through stripper I9 over contacting surfaces 23, such as Raschig rings or bubble plates, and leaves the lower portion of the stripper through line 25, passes through the stripper reboiler 21 wherein it is indirectly heated by steam and thence back to the lower portion of tower I9 through line 29 immediately below the plate 3I. The plate 3| has vapor uptakes 33 but does not permit liquid to flow from the section of the stripper above the plate into the section below the plate. Lean oil is withdrawn from the bottom of the stripper through line 35, passed in indirect heat exchange with fat-oil in the ex-y changer I5, cooled to a temperature of Ff or less in water cooler 31 and returnedto the lean oil accumulator 39. From the accumulator 39 the lean absorption oil is pumped by means of pump 4I through line 1 back to the top of the absorber. Fresh absorber oil is charged to accumulator 39 as required through line 42.

Gases stripped from the absorber oil leave the top of the stripper I9 through line 43, pass through water cooler 45 wherein the heavier coni stituents of the gas are condensed to a liquid and collected in reflux' accumulator 41. The liquefied gas is recycled by means of pump 49 through line: 5I to the top of stripper I9 as reflux. Uncondensed gas is withdrawn from the accumulator 41 through line 53 and may be used for any de-i sired purpose, such as fuel, gasoline blending stock or charging stock for a gas polymerization or polyforming operation.

The gas, stripped of a large portion of its high molecular weight constituents, leaving the topl of the absorber 5 through line I I is charged through line 55 (Figure 2) to a methane heater 51 located in furnace 59. The methane heater may be a heating coil of sufficient length .to heat the gas to a temperature of approximately 900 to 1200o F., but preferably about 10001100 F. In some cases it may be advantageous to heat thegas toI temperatures of the order of 1500o F. or above as a means of supplying heat to the sulfur vapor in the gas-sulfur vapor superheater. In most cases, however, it is advantageous to keep the gas below its threshold cracking temperature under;

the conditions employed. From the outlet of the methane heater, the preheated gas passes through line 6I and joins sulfur vapor at the point 63, and the combined gas-sulfur vapor tion temperature of approximately 950-1300 F., but preferably about 11001175 F.

Instead of mixing the methane with sulfur at the outlet of the sulfur boiler, methane may be introduced into the sulfur stream at the sulfur boiler inlet and the sulfur vaporzed in the presence of methane. When introducing methane into the sulfur boiler inlet, it is preferred to preheat the methane to a temperature sufficient to prevent cooling of the sulfur.

Solid sulfur, preferably in powderedc form is fed from hopper S1 into sulur,` melter 59. The sulfur melter is heated by means of a steam coil 'Il so that the molten sulfur is maintained at a temperature between approximately 250-300 F., and preferably about 270- F. Care should be exercised not to heat the sulfur in melter Se to a` temperature within the high viscosity sulfur range; The molten sulfur is pumped from the melter 69 by means of submerged centrifugal or othersuitable pump 13 through line 15, preferably under a pressure of approximately 50-.100 pounds perv square inch, to sulfur boiler 11.

The pressure under which the molten sulfur is pumped will: depend on the'operating pressure maintained in the reactor and on the mechanical.' design of the unit. The sulfur boiler may be a tube or coil made of alloy or other materials having high resistance to sulfur corrosion, such as, for. example', anv alloycomposed' of 16% to 18% chromium, to- 14%Y nickel, 2% to 3% molybdenum, 2% maximum manganese, 0.1% maxi- 4 suitable catalytic reactor of this type is shown and disclosed in Patent No. 2,149,300.

Where adiabatic operation of the reactor is conducted, the reactor will be well insulated against heat loss and may be lined with a material such as magnesite capable of resisting corrosion of sulfur and sulfur compounds present in the reactor. The reactor may also be constructed mum carbon and the balance iron. Inv the sulfur boilerfll, the sulfur is heated to a temperature sufficient to vaporize it at operating pressures employed, which temperature maybe approximately 85021200.o F., after which the sulfur vapor leaves the sulfur boiler 'H through line 8l and joins the preheated hydrocarbon gas at the point 63 before passingtothe superheater 55, The superheater 65 will also be constructed of. sulfur resistant alloy similar to that used insulfur boiler 11.

The mixing of the sulfur and hydrocarbon vapor before. superheating isv important for the reason that loss of heat in the gas undergoing. reaction is reduced. Sulfur dissociates at high temperatures with absorption of heat, and the amount of dissociation is dependent upon the partial pressure of the sulfur vapor. If sulfur were superheated separately and then mixed with the superheated gas, the partial pressure of the sulfur would be lowered upon mixtureA with the gas, with the result that further dissocationand absorption of heat would occur after the sulfur left the superheater with consequent lowering of temperature of `the reaction mixture below desired reaction temperature. Therefore, by mixing the sulfur vapor and gas before superheating, further dissociation of sulfur vapor occurs in the superheating zone and loss of temperature due to dissociation after superheating and consequent reduction in conversion rate are avoided.

The superheated gas-sulfur stream leaves the superheater 65 through line 83 and passes to the upper portion of reactor 85. Reactor 85 may take the form of a tube or drum. Where iso-thermal operation is used, the reactor 85 is heated sufficiently to maintain the temperature of the reactants and prevent temperature drop through the reactor. Any suitable type of reactor may be used, as, for example, a series of parallel tubes located in a furnace, or a drum containing parallelY tubes anchored at both ends in plates so that hot combustion gas may pass around the tubes with the reactants passing through the tubes. A

sufficient to of corrosion resistant alloy similar to that used in the heating tubes. The reactor is filled with a catalyst capable of accelerating the reaction of sulfur and hydrocarbon to carbon disulfide, such as silica gel, activated alumina, catalytic clays, bauxite, natural or synthetic silica-alumina catalytic compositions, particularly synthetic silicaalumina catalysts containing from,2% to'10%fby Weight of silica, and in general those catalysts disclosed in Thacker Patent 2,330,934,

Where the reactor is operated iso-thermally. the temperature in the reactor will be maintained from 950 to 1300 F;, and preferably be'- tWeen 10001150 F. Where adiabatic oper-ation of the reactor is conducted', it is preferred to charge the reactants to the reactor at va temperature suihciently above the desired reaction temperature so that the average temperature through the reactor Will be approximately the desired temperature. For example, if it is desired to operate at a temperature of approximately 1115u F., and at a pressure of from 20-60' pounds per square inch, the reactants may be fed to the, top of the reaction chamber at a temperature of approximately 1145" F., since a drop in temperature of approximately 30 to F. occurs. through the catalyst bed. When operating adiabatically temperature of approximately 1075 to 11'75" F; may be maintained in the catalyst bed. The size of the reactor and hence the amount of` catalyst needed is deter mined by theV amount of conversion desired and the conditions of operation employed. For the conditions, of operation specied aboveaI space velocity based on hydrocarbon charge onlyv of from 100 to 400 results in good conversion. Space Velocity is defined here as the number of cubic feet of gas at 32 F. and 760 mm. Hg passing over unit volume of catalyst per hour. The amount of sulfur charged may vary, but amounts equal to or in excess of that required for stoichiometric reaction with the above volumes of gas are preferred. The preferred pressure maintained in reactor will be approximately 20 to 60 pounds per square inch. The reactor is preferably operated at a pressure charge the reaction products through the remainder of the apparatus without the necessity of compressing gases. f

Alternatively, the reaction may be carried out at pressures below 20 pounds per square inch. Lower pressures tend to decrease temperature drop across the catalyst bed, especially when operating adiabatically in the lower part of the temperature range. A compressor could be used to attain desired pressures in the carbon disulfide recovery system.

In the reactor 05, the sulfur and hydrocarbons combine to form carbon disulfide and hydrogen sulfide. The proportion of hydrocarbon and sulfur charged to the reactor may vary somewhat, but We prefer to use an amount of sulfur equal to about 10% to 50% by weight in excess yof the stoichiometric amount necessary to react with the hydrocarbon to form carbon disulfide and hydrogen sulfide. The use of excess sulfur is beneficial for several reasons. Because of reaction the heat of reaction would be absorbed` by the excess sulfur. Moreover, the excess sulfur causes more complete reaction of the hydrocarbon and by keeping the content of hydrocarbon in the tail gas low, thenecessity of separating the hydrocarbon from the hydrogen sulfide prior to recovery of sulfur from the hydrogen sulde is avoided.

The reaction products leave the bottom of the reactor 35 throughv line 81 and pass through a waste heat boiler 89 where the gases pass in indirect heat exchange with water and/or steam in order to convert the water to high pressure steam for use in tl boilers and for extraneous use if excess steam` ioavailable. The total rea-ction products leave the waste heat boiler 89 at a temperature of approximately 450 to 500 F., pass through water cooler 3| where the temperature of the reaction products is reduced to approximately 250-300 F., and preferably about 210 F., and the products are then charged to the lower portion of the sulfur-gas separator 83. Instead of using a waste heat boiler and subsequent water cooler for condensing sulfur and cooling products, other arrangements may be used such as nned radiating surfaces and/or conventional Water coolers. The sulfur-gas separator 93 may be a tower containing a series of bubble plates 95 to afford contact between the rising gases and the successive bodies of liquid sulfur, supported on the plates. Other contact surfaces, such as Raschig rings, may be substituted for bubble plates 95, and the separator maintained substantially flooded with liquid sulfur. l Molten sulfur is charged by pump 13 from melter 69 through line 91 to the separator 03. In the separator 33, the major portion of the sulfur contained in the reaction gases is condensed and absorbed in the liquid sulfur. Carbon disulde and hydrogen sulde, together with any unreacted hydrocarbon gas, leave the top of the separator through line 99 and pass to the lower portion of a gas scrubber I0 Molten sulfur is recirculated from the bottom of sulfurgas separator 93 through line |03 back to sulfur melter E9. Alternatively, liquid sulfur may be circulated from the bottom to the top of separator 93, through the line |04 by means of pump |05. The pressure in sulfur-gas separator 93 is ordinarily sufficient tovl force the sulfur from the bottom of the tower back to the melter without the necessity of pumping it; It may be desirable to recycle the sulfur from the bottom of separator 93 to a flash drum |06 maintained at atmospheric pressure in order to permit any carbon disulde which may have been absorbed in the sulfur to flash oilE and thereby avoid the possibility of the carbon disulfide vapor flashing in the melter and causing fire. Any carbon disulde flashed off in the drum |06 is withdrawn through line lll'for recovery, or may be exhausted through the air. The molten sulfur is returned from the ash drum |06 to the sulfur melter through line |09. Appropriate valves H! and H3 are placed in lines H5 and ID3, respectively, in order to divert the sulfur stream either to the hash drum |06 or to the 6 sulfur melter 69. In the gas scrubber |0|, the reaction products from which the bulk of the sulfur has been removed will pass upwardly countercurrent toa stream of scrubber oil in order to remove any remaining sulfur from the reaction products. As scrubber oil, light gas oil or a lubricating oil fraction may be used. The scrubber |0| is provided with Raschig rings H1, or other suitable contacting surfaces. The temperature in the scrubber will be approximately the same as that in separator `S3 and the pressure will be approximately the same as maintained in the reactor. The reaction products denuded of remaining sulfur are withdrawn from the top of gas scrubber lill through line H9 and after being cooled to a temperature of F. or less by means of cooling water in heat exchanger |2| are passed to the gas recovery system. The scrubber oil leaves the bottom of scrubber IBI through water cooler |23 where the temperature of the oil is reduced to 100 F. or less and passes to settling drums |25 and |21 through lines |29 and |3| controlled by valves |33 and |35. Two settling drums are provided in order that sulfur may be permitted to settle from the oil in one drum and the sulfur and oil (optionally) removed from this drum while oil is being recirculated to and from the other drum. Upon cooling the scrubber oil, the sulfur precipitates out of the oil and is withdrawn as a sludge from the bottom of the settlers through lines |31 and |39. Oil is recirculated from the drums through lines IM, H53 and |45. Lines |4| and |43 are controlled by valves |41 and |49 in order to permit shutting 01T one line while oil is recirculated from the other drum. The oil is recirculated back to the scrubber IBI by means of pump |5| through heater |53, wherein the oil is indirectly heated by steam to a temperature of approximately 250-300 F., and preferably about 270 F. Make-up oil may be added through line |54 as required.

In place of the settling drums |25 and |21, lters or centrifuges may be provided to sep--4 arate and remove sulfur from the oil. The scrubber oil may be recycled indefinitely or the oil may be withdrawn from time to time and burned or used for making high sulfur cutting oils or extreme pressure lubricants. The oil is particularly valuable as a cutting oil because of the high sulfur content thereof made possible by the manner in which the sulfur is incorporated in the oil.

Reaction products after leaving gas scrubber through line H9 and after having been cooled to 100 F. or less in exchanger |2| pass through line |55 (Figure 3) into the lower portion of an absorber |51. The absorber is iilled with Raschig rings or other liquid-gas contacting elements. Absorber |51 is preferably maintained at a pres-A sure of approximately 20 to 50 pounds per square inch in order to absorb carbon disulde from the reaction product gases. Lean oil is pumped into the top of the absorber from accumulator |59 through line IEI by'means of pump |63. As absorber oil, heptane or petroleum naphtha having `a boiling range of about 200-400 F. or other fraction boiling above the boiling point of carbon disulfide may be used. Other solvents o'r absorbing mediums such as benzene and o--dichlo-v robenzene may be used. It is preferable to choose an absorber oil which has a boiling point or boiling range not too far above thev boiling point of carbon disulde in order to enable the latter to be readily stripped therefrom. However, heavier absorption oils may be used and stripping carried out with the 'aid of a stripping medium such as steam, methane or other inert gas. The unabsorbedV gas leaves the top o f the absorber through line |65. This gas is composed principally of hydrogen sulfide with a small amount of hydrocarbon gas and about 0.5% or less of carbon disulfide. This gas may be charged to a hydrogen sulfide recovery system wherein the hydrogen sulde is converted to sulfur, or the gas may be used in the manufacture of other chemicals such as sodium sulfide, sodium hydrosulde, zinc sulfide and suluric acid. The rich oil is withdrawn from the bottom of absorber |51 by means of pump |91, passed through steam heater |69 where the rich oil is preheated to a suitable temperature, as for example, 200-325 F. and charged to the middle section of stripper |1|. Stripper |1| is provided with Raschig rings |13 or other liquid-gas contact elements. Carbon disulfide is stripped from the absorber oil and passes from the top of the stripperthrough'line |15, water cooler or condenser |11 where the temperature is reduced to 100 F. or less, to accumulator |19. Any gas and/or vapor which remains uncondensed leaves the accumulator |19 through line I8! and is returned to the inlet ofthe absorber 51 through line |95. The stripper |1| is preferably operated at a pressure slightly above the pressure in the.

absorber |51, as, for example, 25 to 55 pounds per square inchy in order to avoid the necessityl of compressing the gas returned through line ||l| to the scrubber.

The absorber oil is withdrawn from the plate |83 in the bottom portion of stripper |1| through line |85 and charged to reboiler |81 and thence returned through line |89 to the section of the stripper below the plate |83. Plate |83 is provided with vapor uptakes |9|. Lean absorber oil is withdrawn from the bottom of stripper |1| through line |93, cooled in water cooler |95 to a temperature below 100 F. and returned to accumulator |59. It will be apparent that the rich oil from absorber |51 can be used to partially cool the lean oil from stripper |1| by providing a suitable heat exchanger. Fresh absorber liquid is added to accumulator |59 as required through line |95.

Liquid carbon disulde is withdrawn from accumulator |19 through line |91 and charged by means of pump |99 to stabilizer 20|. A portion of the carbon disulfide is returned through line 203 to the upper portion of stripper |1| as reflux. The stabilizer 20| is operated at pressures of 20 pounds per square inch gauge or above and preferably in the range of 50-150 pounds. The temperature in the bottom of the stabilizer is that needed to effectively boil the carbon disulde and free it of hydrogen sulfide and hydrocarbon gas under the conditions of operation. The stabilizer 20| is equipped with contact surfaces 204, such as Raschig rings, with a plate 205 having vapor uptakes 201 and a reboiler 209. In the stabilizer 20|, any hydrogen sulfide or hydrocarbon gas absorbed in the carbon disulde is boiled oi and passes overhead through line 2|| through water cooler 2|3. A small amount of carbon disulde passes overhead, condensed in part in cooler 2|3, and col.-4 lected in accumulator 2|5. The condensate from accumulator 2| 5 is returned to the top of the stabilizer through line 2|1 by means of pump 2| 9. The uncondensed gases and vapors are Withdrawn from the accumulator 2|5 through line 22| and recycled to the inlet of absorber |51 through line |55. The bottoms from the stabilizer 20| are withdrawn through a pressure control valve 202 and charged through line 223 with the necessary heating or cooling, to the middle portion of fractionating column 225 from which the carbon disulde is taken overhead through line 221, condensed in water cooler 229 and collected in accumulator 23| as finished product. Any bottoms, such as absorption oil, which may have passed overhead with the carbon d1- sulde from stripper |1| are withdrawn from the bottom of the fractionator 225 through line 232. Fractionator 225 is equipped with contact surfaces 233 such as Raschig rings, a separator plate 235 having vapor uptakes 231 and a reboiler 239. Fractionator 225 is preferably operated at atmospheric or below superatmospheric pressure. The finished carbon disulfide is withdrawn from the accumulator by means of pumps 24| through line 243 to storage. A portion o1 the carbon disulde may ha recirculated through line 245 as reux to tha-top of the fractionator 225.

It will be understood that the process is not limited to the flow described and the apparatus shown in the recovery system. Variations in both flow and equipment can be made to suit particular conditions of operation. For examplc, when operating under pressure. a portion of the carbon disulde will condcdnse in cooler |2 It might be expedient, therefore, when operating under pressure. to provide an accumulator to which the products leaving cooler |2| could be sent in order to separate the condensed carbon disulfide and then charge it directly to the sitabilizer 20|.

Likewise, by equipping absorber |51 with a reboiler so that hydrogen sulde and methane can be completely removed from the liquid, the stabilizer 20| can be dispensed with.

It will be apparent to those skilled in the art that the various pieces of equipment are shown diagrammatically. The invention is not limited to the use of any particular type of equipment. For example, although once-through reboilers have been shown, kettle-type reboilers may be used in place thereof. Moreover, strippers may be used which employ live steam as stripping medium. Such other variants as are Within the skill of the art are implicit within the disclosure.

The following examples are given to demon-l strate the invention.

Example 1.--Natural gas was charged to the gas preparation portion of the system and con.- tacted in the absorber with No. 2 furnace oil. The gas leaving the absorber had a methane content of between 97798 mol per cent, the balance being principally ethane with less than 1% of propane and higher molecular weight hydrocarbons. The prepared natural gas was charged to the gas heater wherein the gas was heated to a temperature of approximately 1090 F. The gas was charged to the heater at a rate of 142 cu. ft. per hour. Sulfur was charged at a rate of 64.7 pounds per hour to the sulfur boiler and there heated to a temperature of approximately 1050 F. The mol ratio of S2 vapor to gas charged was 2.55. The sulfur vapors and preheated gas were mixed and charged to the superheater wherein the mixture was heated to a temperature of approximately 1120 F. The mixed gas-sulfur stream was maintained in the catalyst bed at an average temperature of ap.-

9 proximately 1112 F. 'I'he operation was conducted iso-thermally, the reaction chamber being electrically heated sufficiently to maintain the catalyst bed at a desired reaction temperature. The reactor used was an alloy tube approximately 44 inches in length and 6 inches I. D., placed in vertical position. The reactor contained a perforated plate adjacent the bottom thereof, upon which a three-foot bed of catalyst was retained. The catalyst space was nlled with 24.8 pounds of 6 mesh silica gel occupying a space of 0.59 cu. ft. The pressure at the superheater outlet and in the reactor was approximately 44 pounds per square inch gauge. The run was conducted for a period of 12 hours during which period the average production of carbon disulfide was 28 pounds per hour. The carbon disulde recovered was 90% of the theoretical amount based on the gas charged.

Example 2.--A second run was conducted in the same apparatus as that used for the run in Example 1, except that the reactor Was operated under adiabatic conditions. Only sunicient heat was applied to the outside of the reactor to prevent loss of heat through the reactor Wall. In this run the prepared natural gas was preheated to a temperature of 10.95 F. and the sulfur vapor was heated to 1050Q F. before being mixed with the preheated gas. The mixed stream was superheated to a temperature of 1140 F. at which temperature it left the superheater under pressure of 46 pounds per square inch gauge. The mixed gas-sulfur vapor stream entered the catalyst lbed at about 46 pounds per square inch pressure and at a temperature of 1132 F., and left the catalyst bed at a`-tempera ture of approximately 1104" F. so that the temperature drop through the bed was approximately 28 F. In this run, the sulfur Was charged to the sulfur boiler at the rate of 66.4 pounds per hour, and the gas was charged at the rate of 139 cu. ft. per hourto the gas preheater. The mol ratio of S2 vapor to gas charged was 2.68. The run was conducted for a period of 12 hours during Which period the average production of carbon disulde was 27.5 pounds per hour, with a conversion of 89% of the theoretical amount of carbon disulfide based on the hydrocarbon gas charged.

In preparing the gas for the runs in Examples 1 and 2, No. 2 furnace oil Was used in the feed preparation absorber; a 50-50 mixture of benzol and Stoddard solvent was used in the recovery system absorber; and No. 2 paraiiin oil Was used in the gas scrubber to remove sulfur from the reaction gases.

What is claimed:

1. A process for preparing carbon disulfide comprising preheating natural gas low in Ca and heavier hydrocarbons to a temperature above the boiling point of sulfur but below reaction temperature, vaporizing sulfur, mixing vaporized sulfur with preheated gas in such proportions that sulfur is present in an amount of about to 50% by Weight in excess of the stoichiometric amount required to form carbon disulde and hydrogen sulde With said gas, heating the mixture to a temperature sufliciently above reaction temperature to give an average reaction temperature under adiabatic reaction conditions approximately equal to the desired reaction temperature, contacting the heated mixture in an adiabatic reaction zone with a catalyst selected from the group consisting of silica gel, activated alumina, synthetic silicaalumina catalysts, catalytic absorptive clays and bauxite at a temperature of approximately 1075 to 1175 F. for a period of time suflicient to produce a substantial amount of carbon disulfide, cooling the reaction products to a temperature above the melting point of sulfur but below the temperature of viscous sulfur, contacting the partially cooled reaction vapors With molten sulfur to remove sulfur from said vapors and recovering carbon disulfide from said vapors.

2. A process for preparing carbon disulfide comprising heating a mixture of sulfur vapor and hydrocarbon gas having a high methane content and a 10W content of C3 and heavier hydrocarbons, in which mixture the sulfur content is about 10 to 50% by Weight in excess of the stoichiometric amount required to form carbon disulfide and hydrogen suliide, to a temperature suiiicient to maintain the mixture at an average temperature of approximately 1075 to 1175 F. in an adiabatic reaction Zone, contacting the heated mixture in an adiabatic reaction zone with a carbon disulde-promoting catalyst for a period of time sufficient to produce a substantial amount of carbon disulfide and recovering carbon disulfide from the reaction products.

3. Process in accordance with claim 2 in which the mixture of sulfur vapor and hydrocarbon gas is heated to a temperature about 30 to 70 F. above the average reaction temperature to be maintained in the reaction zone.

4. Process in accordance with claim 2 in which the sulfur vapor-hydrocarbon gas mixture is charged to the reaction zone at a super-atmospheric pressure up to about 60 pounds per square inch.

5. Process in accordance with claim 2 in which the carbon disulde-promoting catalyst is a substance from the group consisting of silica gel, activated alumina, synthetic silica-alumina, bauxite and catalytic adsorptive clays.

HILLIs o. FOLKINs. CHARLES A. PORTER.. ELMER MILLER. HARVEY HENNIG.

REFERENCES CITED The following references are of record in the file of this patent:`

UNITED STATES PATENTS Number Name Date 1,735,409 Pier Nov. 12, 1929 2,187,393 De Simo Jan. 16, 1940 2,330,934 Thacker 1 Oct. 5, 1943 2,386,202 Fernelius et al. Oct. 9, 1945 2,411,236 Thacker NOV. 19, 1946 2,450,658 Hansford et al Oct. 5, 1948 2,450,687 Rasmussen et al. Oct. 5, 1948 2,474,067 Preisman June 21, 1949 2,487,039 Belchetz Nov. 8, 1949 FOREIGN PATENTS Number Country Date 331,734 Great Britain July 10, 1930 OTHER REFERENCES Mellor: Comprehensive 'Ireatise on Inorganic and .Theoretical Chemistry, (1930), vol. 10, pages 43, 60, 98 and 99. 

1. A PROCESS FOR PREPARING CARBON DISULFIDE COMPRISING PREHEATING NATURAL GAS LOW IN C3 AND HEAVIER HYDROCARBONS TO A TEMPERATURE ABOVE THE BOILING POINT OF SULFUR BUT BELOW REACTION TEMPERATURE, VAPORIZING SULFUR, MIXING VAPORIZED SULFUR WITH PREHEATED GAS IN SUCH PROPORTIONS THAT SULFUR IS PRESENT IN AN AMOUNT OF ABOUT 10% TO 50% BY WEIGHT IN EXCESS OF THE STOICHIOMETRIC AMOUNT REQUIRED TO FORM CARBON DISULFIDE AND HYDROGEN SULFIDE WITH SAID GAS HEATING THE MIXTURE TO A TEMPERATURE SUFFICIENTLY ABOVE REACTION TEMPERATURE TO GIVE AN AVERAGE REACTION TEMPERATURE UNDER ADIABATIC REACTION CONDITIONS APPROXIMATELY EQUAL TO THE DESIRED REACTION TEMPERATURE, CONTACTING THE HEATED MIXTURE IN AN ADIABATIC REACTION ZONE WITH A 